US20110028671A1 - Process for producing high strength polyethylene film - Google Patents

Process for producing high strength polyethylene film Download PDF

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Publication number
US20110028671A1
US20110028671A1 US12/935,352 US93535209A US2011028671A1 US 20110028671 A1 US20110028671 A1 US 20110028671A1 US 93535209 A US93535209 A US 93535209A US 2011028671 A1 US2011028671 A1 US 2011028671A1
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Prior art keywords
polyethylene
films
process according
temperature
disentangled
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US12/935,352
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US8188207B2 (en
Inventor
Jan Adolph Dam Backer
Bart Clemens Kranz
Benjamin Slager
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Novameer BV
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Novameer BV
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Assigned to NOVAMEER B.V. reassignment NOVAMEER B.V. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KRANZ, BART CLEMENS, SLAGER, BENJAMIN, BACKER, JAN ADOLPH DAM
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B13/00—Conditioning or physical treatment of the material to be shaped
    • B29B13/02—Conditioning or physical treatment of the material to be shaped by heating
    • B29B13/021—Heat treatment of powders
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0658—PE, i.e. polyethylene characterised by its molecular weight
    • B29K2023/0683—UHMWPE, i.e. ultra high molecular weight polyethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene

Definitions

  • the present invention pertains a process for producing a high strength polyethylene film, filament or tape.
  • Ultra high molecular weight polyethylene having a molecular weight in the range of 400000 g/mol up to several million g/mol.
  • Ultra high molecular weight polyethylene is very difficult to process into high strength film, filaments or tapes (e.g. from slitted film) without using solvent.
  • the difficulty in processing is caused by entanglements in the very long crystal network.
  • ultra high molecular weight polyethylene (UHMWPE) is often dissolved in suitable solvents, like decalin and paraffin, in order to disentangle the network. But after being processed into a film, filament or tape the solvent has to be fully removed. This is very difficult and expensive, and a solvent content below 0.1% is nearly never achieved.
  • Some solvent-free developments or processing routes e.g. from Nippon Oil, ITS-Tensylon or DSM (see e.g. EP 1627719) use UHMWPE in the form of a powder, scattered onto a high pressure continuous isobar steel belt press to make a compacted film. This film can be drawn in different steps at an elevated temperature into a high strength film or tape.
  • the thickness and evenness of the scattered powder layer, the accurate pressure and temperature in the belt press are all key factors to achieve optimum results with regard to the strength and modulus of the resulting UHMWPE product.
  • UHMWPE Ultra High Density Polyethylene
  • a well known method for UHMWPE to be processed into films is skiving thin layers from sintered sheets or round blocks. These films are generally used for anti adhesive surfaces or highly abrasive resistant skins like ski- or snowboard gliding surfaces in a thickness between 0.10 mm and up to 4 mm. For those UHMWPE films there is no drawing or stretching needed. For these purposes the ultimate tensile strength and e-modulus are not the desired properties, merely the smoothness and abrasion resistance.
  • ⁇ max is the maximum draw ratio
  • K is the proportionality constant
  • M e is the molar mass between entanglements.
  • a high strength polyethylene film or tape preferably exhibits a tensile strength of at least 1200 MPa and a tensile modulus of at least 40 GPa.
  • the polyethylene used in the process according to the invention has a molecular weight of at least 100.000 g/mol, more preferably 500.000 g/mol and most preferably at least 1.000.000 g/mol.
  • the polyethylene may also be a mixture of polyethylenes of different molecular weight e.g. a bimodal polyethylene comprising two different molecular weight polyethylenes.
  • the quantity of disentangled polyethylene is preferably in the form of a powder.
  • the temperature of the process according to the invention is between ⁇ -relaxation temperature and T m pE ⁇ 10° C., more preferably between 100° C. and 130° C.
  • the applied pressure is at least 50 bar, more preferably at least 100 bar, most preferably at least 200 bar or even 500 bar.
  • a block is a compacted volume of a powder in a regular shape e.g. a disc shape, preferably of thickness of at least 5 mm.
  • the resulting block is ductile even though pressed below the melting temperature.
  • a block made of entangled polyethylene powder pressed below the melting temperature could not be skived in a subsequent step due to its brittle nature.
  • the film or tape skived off the block is preferably between 0.1 mm to 10 mm thick, more preferably between 1 mm and 3 mm thick.
  • the final product obtained by the process according to the present invention may exhibit a thickness of less than 1000 ⁇ m, preferably less than 100 ⁇ m, more preferably less than 30 ⁇ m.
  • the total draw ratio of the film or tape is preferably at least 1:50, more preferably at least 1:100, most preferably 1:150.
  • a so-called disentangled or nascent polyethylene will have hardly or no entanglements of the individual chains, and therefore the crystals can be unfolded easily by drawing the material above the a-relaxation temperature of 80-90° C.
  • the present invention is an alternative route to achieve highly drawable films by combining the pressing of disentangled polyethylene powder in thick blocks as now used for ski/snowboard surfaces, but at a much lower temperature than usual i.e. between 80° C. and 130° C. instead of the standard temperature well above 150° C., often even 180° C. or higher.
  • the powder is not molten, but compacted under sufficient pressure at elevated temperature, in order to avoid chain entanglements that usually occur during the melting and sintering.
  • the produced blocks can then be skived into thin films or tapes which can than be drawn or ultra-drawn into high strength, high modulus films or tapes.
  • the present process is much simpler and therefore cost effective than the current processes using solvents or double belt press.
  • the double belt press process requires a very accurate process conditions.
  • the skived, yet still disentangled polyethylene film produced according to the invention can preferably be drawn in a multi stage drawing step, i.e. different consecutive drawing stages and temperatures. Good results were achieved e.g. with the following steps:
  • Total draw ratio of this particular set up is 130 times the original isotropic, disentangled polyethylene film produced according to the invention, which started as a 2.5 mm thick film, skived from a block.
  • the compression conditions were: pressure in the mould 180 bar for 10 hours at 120° C.
  • the first step can, rather than drawing only, also be a combined process using calendar pressure rolls plus drawing godets behind it. This way, no or very little width is lost of the film, the final result is a thinner film, which is also easier to take up the correct drawing temperature.
  • the initial draw can start at a temperature as low as 90° C.
  • films or tapes produced in a process according to the invention can be used in antiballistic applications as well as in composite applications, stand-alone or in combination with other materials.

Abstract

Process for producing high strength polyethylene films or tapes comprising the steps of: providing a quantity of disentangled polyethylene, applying a pressure of at least 20 bar to the quantity of disentangled polyethylene and a temperature between the α-relaxation temperature and the melting temperature of the disentangled polyethylene Tm PE resulting in a block of disentangled polyethylene, skiving a film or tape off the block of disentangled polyethylene and, drawing said film or tape in a single or multi stage drawing step at a total draw ratio of at least 1:20.

Description

  • The present invention pertains a process for producing a high strength polyethylene film, filament or tape.
  • Currently high strength polyethylene film, filament or tape is produced from ultra high molecular weight polyethylene (UHMWPE) having a molecular weight in the range of 400000 g/mol up to several million g/mol.
  • Commercially available ultra high molecular weight polyethylene (UHMWPE) is very difficult to process into high strength film, filaments or tapes (e.g. from slitted film) without using solvent. The difficulty in processing is caused by entanglements in the very long crystal network.
  • For this reason, the ultra high molecular weight polyethylene (UHMWPE) is often dissolved in suitable solvents, like decalin and paraffin, in order to disentangle the network. But after being processed into a film, filament or tape the solvent has to be fully removed. This is very difficult and expensive, and a solvent content below 0.1% is nearly never achieved.
  • Some solvent-free developments or processing routes e.g. from Nippon Oil, ITS-Tensylon or DSM (see e.g. EP 1627719) use UHMWPE in the form of a powder, scattered onto a high pressure continuous isobar steel belt press to make a compacted film. This film can be drawn in different steps at an elevated temperature into a high strength film or tape.
  • The thickness and evenness of the scattered powder layer, the accurate pressure and temperature in the belt press are all key factors to achieve optimum results with regard to the strength and modulus of the resulting UHMWPE product.
  • On the other hand, a well known method for UHMWPE to be processed into films is skiving thin layers from sintered sheets or round blocks. These films are generally used for anti adhesive surfaces or highly abrasive resistant skins like ski- or snowboard gliding surfaces in a thickness between 0.10 mm and up to 4 mm. For those UHMWPE films there is no drawing or stretching needed. For these purposes the ultimate tensile strength and e-modulus are not the desired properties, merely the smoothness and abrasion resistance.
  • Due to the entangled crystal network of these films skived from UHMWPE blocks, drawing this skived film/sheet into high strength film is impossible. Draw ratios of λ 1:10 or higher cannot be achieved with UHMWPE having an entangled crystal network. However, high strength applications require draw ratios λ of the film in the range of 1:10 up to 1:100 or even 1:300.
  • The maximum possible draw ratio for a standard sintered powder of UHMWPE λmax is given in the following equation:

  • λmax =K(M e)1/2
  • where λmax is the maximum draw ratio, K is the proportionality constant and Me is the molar mass between entanglements.
  • For entangled UHMWPE the maximum draw ratio is found to be below 10.
  • It is therefore an object of the present invention to provide a process for producing high strength polyethylene films, filaments or tapes in which the disadvantages of the prior art are at least reduced.
  • This object is achieved by a process for producing high strength polyethylene films or tapes comprising the steps of
      • providing a quantity of disentangled polyethylene,
      • applying a pressure of at least 20 bar to the quantity of disentangled polyethylene and a temperature between the α-relaxation temperature and the melting temperature of the disentangled polyethylene Tm PE resulting in a block of disentangled polyethylene
      • skiving a film or tape off the block of disentangled polyethylene and
      • drawing said film or tape in a single or multi stage drawing step at a total draw ratio of at least 1:20.
  • A high strength polyethylene film or tape preferably exhibits a tensile strength of at least 1200 MPa and a tensile modulus of at least 40 GPa.
  • Preferably the polyethylene used in the process according to the invention has a molecular weight of at least 100.000 g/mol, more preferably 500.000 g/mol and most preferably at least 1.000.000 g/mol. The polyethylene may also be a mixture of polyethylenes of different molecular weight e.g. a bimodal polyethylene comprising two different molecular weight polyethylenes.
  • The quantity of disentangled polyethylene is preferably in the form of a powder.
  • Preferably the temperature of the process according to the invention is between α-relaxation temperature and Tm pE−10° C., more preferably between 100° C. and 130° C.
  • Preferably the applied pressure is at least 50 bar, more preferably at least 100 bar, most preferably at least 200 bar or even 500 bar.
  • A block is a compacted volume of a powder in a regular shape e.g. a disc shape, preferably of thickness of at least 5 mm.
  • The resulting block is ductile even though pressed below the melting temperature. A block made of entangled polyethylene powder pressed below the melting temperature could not be skived in a subsequent step due to its brittle nature.
  • The film or tape skived off the block is preferably between 0.1 mm to 10 mm thick, more preferably between 1 mm and 3 mm thick. The final product obtained by the process according to the present invention may exhibit a thickness of less than 1000 μm, preferably less than 100 μm, more preferably less than 30 μm.
  • The total draw ratio of the film or tape is preferably at least 1:50, more preferably at least 1:100, most preferably 1:150.
  • Recently, there are processes developed that allow the production of non entangled or disentangled polyethylene powder with the polyethylene having a molecular weight in the range of 105 to 107 g/mol. This process makes use of special, sophisticated single site catalysts in addition to the right polymerisation temperature and pressure, during the polymerisation of the polyethylene powder.
  • A so-called disentangled or nascent polyethylene will have hardly or no entanglements of the individual chains, and therefore the crystals can be unfolded easily by drawing the material above the a-relaxation temperature of 80-90° C.
  • Rather than scattering very accurately a UHMWPE powder onto a continuous steel belt, the present invention is an alternative route to achieve highly drawable films by combining the pressing of disentangled polyethylene powder in thick blocks as now used for ski/snowboard surfaces, but at a much lower temperature than usual i.e. between 80° C. and 130° C. instead of the standard temperature well above 150° C., often even 180° C. or higher. In the process according to the present invention the powder is not molten, but compacted under sufficient pressure at elevated temperature, in order to avoid chain entanglements that usually occur during the melting and sintering. The produced blocks can then be skived into thin films or tapes which can than be drawn or ultra-drawn into high strength, high modulus films or tapes.
  • The present process is much simpler and therefore cost effective than the current processes using solvents or double belt press. The double belt press process requires a very accurate process conditions.
  • The skived, yet still disentangled polyethylene film produced according to the invention can preferably be drawn in a multi stage drawing step, i.e. different consecutive drawing stages and temperatures. Good results were achieved e.g. with the following steps:
  • 1st draw λ=6, temperature 136-140° C.;
  • 2nd draw λ=4, temperature 144-146° C.
  • 3rd draw λ=3, temperature 148-150° C.;
  • 4th draw λ=1.8, temperature 150-153° C.
  • Total draw ratio of this particular set up is 130 times the original isotropic, disentangled polyethylene film produced according to the invention, which started as a 2.5 mm thick film, skived from a block. The compression conditions were: pressure in the mould 180 bar for 10 hours at 120° C.
  • The first step can, rather than drawing only, also be a combined process using calendar pressure rolls plus drawing godets behind it. This way, no or very little width is lost of the film, the final result is a thinner film, which is also easier to take up the correct drawing temperature.
  • More drawing steps, different drawing ratios and temperatures can be used to achieve the total drawing. The initial draw can start at a temperature as low as 90° C.
  • Tensile strengths of this ultra drawn film above 1650 MPa and tensile moduli above 95 GPa can be achieved.
  • The films or tapes produced in a process according to the invention can be used in antiballistic applications as well as in composite applications, stand-alone or in combination with other materials.

Claims (12)

1. Process for producing high strength polyethylene films or tapes comprising the steps of
providing a quantity of disentangled polyethylene,
applying a pressure of at least 20 bar to the quantity of disentangled polyethylene and a temperature between an α-relaxation temperature and a melting temperature of the disentangled polyethylene (Tm PE) resulting in a block of disentangled polyethylene.
skiving a film or tape off the block of disentangled polyethylene, and
drawing said film or tape in a single or multi stage drawing step at a total draw ratio of at least 1:20.
2. Process according to claim 1, wherein the temperature for forming the block of disentangled polyethylene is between the α-relaxation temperature and Tm PE−10° C.
3. Process according to claim 1, wherein the temperature for forming the block of disentangled polyethylene is between 100° C. and 130° C.
4. Process according to claim 1, wherein the high strength polyethylene films or tapes exhibit a tensile strength of at least 1200 MPa and a tensile modulus of at least 40 Gpa.
5. An antiballistic product comprising the films or tapes produced in the process according to claim 1.
6. A composite product comprising the films or tapes produced in the process according to claim 1.
7. An antiballistic product comprising the films or tapes produced in the process according to claim 2.
8. An antiballistic product comprising the films or tapes produced in the process according to claim 3.
9. An antiballistic product comprising the films or tapes produced in the process according to claim 4.
10. A composite product comprising the films or tapes produced in the process according to claim 2.
11. A composite product comprising the films or tapes produced in the process according to claim 3.
12. A composite product comprising the films or tapes produced in the process according to claim 4.
US12/935,352 2008-04-29 2009-04-21 Process for producing high strength polyethylene film Expired - Fee Related US8188207B2 (en)

Applications Claiming Priority (4)

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EP08155406 2008-04-29
EP08155406 2008-04-29
EP08155406.5 2008-04-29
PCT/EP2009/054726 WO2009132990A1 (en) 2008-04-29 2009-04-21 Process for producing high strength polyethylene film

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US13/420,521 Continuation US8273839B2 (en) 2008-04-29 2012-03-14 Process for producing high strength polyethylene film

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EP (1) EP2274365A1 (en)
JP (1) JP5349585B2 (en)
KR (1) KR20110007156A (en)
CN (1) CN102015847B (en)
RU (1) RU2489453C2 (en)
WO (1) WO2009132990A1 (en)

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US11135805B2 (en) * 2012-06-14 2021-10-05 The Boeing Company Multi-component films

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US7976932B1 (en) * 2007-04-13 2011-07-12 BAE Systems Tensylon H.P.M, Inc. Ballistic-resistant panel including high modulus ultra high molecular weight polyethylene tape
WO2010079174A2 (en) * 2009-01-09 2010-07-15 Teijin Aramid B.V. Polyethylene film and method for the manufacture thereof
US8579325B2 (en) 2010-11-09 2013-11-12 Salflex Polymers Ltd. Active bolster
US9254808B2 (en) 2011-02-07 2016-02-09 Salflex Polymers Limited Active bolster assembly
US20170373360A1 (en) * 2016-06-27 2017-12-28 Ei Du Pont De Nemours And Company Articles containing a heat source and a heat spreader

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CN102015847A (en) 2011-04-13
RU2489453C2 (en) 2013-08-10
KR20110007156A (en) 2011-01-21
JP5349585B2 (en) 2013-11-20
RU2010148415A (en) 2012-06-10
US8273839B2 (en) 2012-09-25
US20120172565A1 (en) 2012-07-05
JP2011518933A (en) 2011-06-30
WO2009132990A1 (en) 2009-11-05
US8188207B2 (en) 2012-05-29
EP2274365A1 (en) 2011-01-19
CN102015847B (en) 2014-04-16

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